Method to increase the lithographic process window of extreme ultra violet negative tone development resists

ABSTRACT

A patterning method that includes providing an amorphous semiconductor surface to be patterned, and terminating the amorphous semiconductor surface by forming silicon-hydrogen (Si—H) on the surface to be patterned. A photoresist is formed on the surface to be patterned. The photoresist is then lithographically patterned using an extreme ultra violet (EUV) method. A photoresist is then developed on the surface to be patterned using negative tone development (NTD).

BACKGROUND Technical Field

The present invention generally relates to lithographic materials forextreme ultraviolet (EUV) lithography, and more particularly toinorganic hardmask processing used in EUV lithography.

Description of the Related Art

Semiconductor fabrication typically involves transfer of a pattern froma mask to a resist using lithography, and transfer of the pattern fromthe resist to a hardmask through etching. The pattern can then betransferred from the hardmask to a semiconductor material throughfurther etching processes. In general, photolithography (in contrast toe-beam lithography, for example) uses light to form an image of the maskon a photoresist material, where the incident light can cause a photoreaction. Light for photolithography has progressed from wavelengths inthe range of 436 nm (blue light) to 365 nm (near ultraviolet (UV)) to248 nm (deep UV) to a wavelength of 193 nm. The wavelength of light hasmoved to smaller and smaller wavelengths in part because the smallestfeature size that can be printed is determined in part by thewavelength. λ of the light used. Another factor that can affect thesmallest printed feature size is the numerical aperture, NA, of theprojection optics. The depth-of-focus (DOF) is also determined by λ andthe numerical aperture NA, which is also typically a factor in resolvingsmall features. The DOF can relate to a visible change in the imagerelated to exposure dose, line width, sidewall angle, and resist loss.As feature sizes decrease, their sensitivity to focus errors increases.

In extreme ultraviolet lithography (EUVL) the extreme ultraviolet light(which also may be referred to as soft x-ray) has wavelengths from 124nm down to 10 nm, and in particular for intended semiconductorprocessing, about 13.5 nm, as generated by a laser-pulsed tin (Sn)plasma source. The 13.5 nm EUV light is currently the focus of the nextgeneration of photolithography tools and processes.

An original image of the features to be formed on a substrate istypically written on a lithography mask, unlike previous longerwavelength light used for lithography, however, EUV light is stronglyabsorbed by almost all materials. Transmission (i.e., refractive) masks,therefore, cannot be used, and approaches using reflective componentsfor the optics and mask are instead being developed.

The image of the mask features is intended to be transferred to aphotoresist on the substrate. In the past photoresists have beenpositive resists in which the exposed area is made soluble in thedeveloper or negative resists in which the exposed area is madeinsoluble to the developer. As the wavelength of light becomes smaller,new photoresist materials are also needed. For example, it has beendetermined that a need exists for ultrathin, e.g., less than 5 nm,inorganic hardmask. e.g., amorphous Si (α-Si) and low temperature oxide(LTO), as a direct etch transfer layer for EUV patterning. In comparisonto spin on hybrid hardmasks, e.g., SiARC, in future hardmasksimprovements are desired in resist thickness budget, higher etchselectivity, lower line width roughness (LWR), improved defectelimination, and wet strippability.

SUMMARY

The methods and structures described herein provide for an ultrathin,e.g., less than 5 nm, inorganic hardmask, e.g., amorphous Si (α-Si) orlow temperature oxide (LTO), as a direct etch transfer for layer for EUVpatterning. The masks provided herein provide an improvement in resistthickness budget, higher etch selectivity, lower line width roughness(LWR), improved defect elimination, and wet strippability. This isprovided by treating a semiconductor surface. e.g., amorphous silicon(α-Si), to terminate the semiconductor surface with silicon-hydrogen(Si—H) bonds. To terminate the semiconductor surface with siliconhydrogen (Si—H) bonds, a diluted hydrofluoric acid (dHF) may be appliedto the semiconductor surface prior to forming the photoresist layer. Ina following process step, the photoresist layer may be patterned usingnegative tone development (NTD) methods.

In one embodiment, a patterning method is provided that includesproviding an amorphous semiconductor surface to be patterned, andterminating the amorphous semiconductor surface by formingsilicon-hydrogen (Si—H) bonds on the surface to be patterned. Aphotoresist is formed on the surface to be patterned. The photoresist isthen lithographically patterned using an extreme ultra violet (EUV)method. A photoresist is then developed on the surface to be patternedusing negative tone development (NTD).

In one embodiment, a patterning method is provided that includesproviding an amorphous semiconductor surface to be patterned. Applying adilute hydrofluoric acid (dHF) to the surface to be patterned toterminate the amorphous semiconductor surface by formingsilicon-hydrogen (Si—H) bonds. A photoresist is formed on the surface tobe patterned. The photoresist is then lithographically patterned usingan extreme ultra violet (EUV) method. A photoresist is then developed onthe surface to be patterned using negative tone development (NTD).

In yet another embodiment, an etch process is provided. In oneembodiment, the method may being with providing an amorphoussemiconductor surface to be etched, and terminating the amorphoussemiconductor surface by forming silicon-hydrogen (Si—H) bonds on thesurface to be patterned. A photoresist is formed on the surface to bepatterned. The photoresist is then lithographically patterned using anextreme ultra violet (EUV) method. A photoresist is then developed intoa mask on the surface to be patterned using negative tone development(NTD). The portions of the amorphous semiconductor surface exposed bythe mask are then etched, while the portions of the amorphoussemiconductor layer that are underlying the mask are not etched.

These and other features and advantages will become apparent from thefollowing detailed description of illustrative embodiments thereof,which is to be read in connection with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The following description will provide details of preferred embodimentswith reference to the following figures wherein:

FIG. 1 is a flow diagram illustrating one embodiment of an etch methodusing the photolithography process that includes a step of treating theamorphous silicon surface to be etched to terminate the surface withsilicon-hydrogen (Si—H) bonds prior to forming a photoresist layer onthe surface to be patterned.

FIG. 2 is a side cross-sectional view depicting one embodiment ofproviding an amorphous semiconductor surface to be etched, andterminating the amorphous semiconductor surface by formingsilicon-hydrogen (Si—H) bonds on the surface to be patterned, inaccordance with one embodiment of the present disclosure.

FIG. 3 is a side cross-sectional view depicting forming a photoresist onthe surface to be patterned.

FIG. 4 is a side cross-sectional view depicting lithographicallypatterning the photoresist layer using an extreme ultra violet (EUV)method.

FIG. 5 is a side cross-sectional view depicting a photoresist beingdeveloped into a mask on the surface to be patterned using negative tonedevelopment (NTD).

FIG. 6A is a scanning electron microscope (SEM) image of a negative tonedeveloped resist that was formed on an amorphous silicon surface thatwas pretreated with hexamethyldisilazane (HDMS) prior to forming thephotoresist layer.

FIG. 6B is a scanning electron microscope (SEM) image of a negative tonedeveloped resist that was formed on an amorphous silicon surface thatwas pretreated with dilute hydrofluoric acid (dHF) prior to forming thephotoresist layer, in accordance with one embodiment of the presentdisclosure.

FIG. 7 is a side cross-sectional view depicting one embodiment ofetching the exposed portions of the amorphous semiconductor surface,while the portions of the amorphous semiconductor layer that areunderlying the mask are not etched.

DETAILED DESCRIPTION

Principles and embodiments of the present invention relate generally tofabricating microelectronics structures, and the resulting structuresformed thereby, using extreme ultraviolet (EUV) lithographic processes.Patterning of small features generated by extreme ultraviolet (EUV)lithography can be limited by a variety of factors, from the photoresistover the substrate to the developer. For example, it has been determinedthat the adhesion performance between prior photoresist compositions andhardmasks can hinder pattern fidelity. Patterning processes are alsoimpacted by tool and mask limitations. With the always shrinkingdimensions of features, and resist thickness, the choice of thesubstrate used to print the resist onto is important for a successfulpattern transfer into the lower layers of the stack. While spin-onsilicon materials, such as silicon anti-reflective coating (SiARC),typically offer good resist adhesion, their etch resistance for patterntransfer is inferior to inorganic materials, such as silicon oxide(SiO₂), silicon nitride or even amorphous silicon (α-Si). However,inorganic surfaces typically lead to pattern collapse or lift off due topoor resist adhesion typically during development.

Typically, for conventional lithographic methods, priming is done usinghexamethyldisilazane (HMDS) in order to improve mask adhesion andpatterning performance on silicon, e.g., amorphous silicon (α-Si) orcrystalline silicon (c-Si), or silicon oxide (SiO₂), e.g., lowtemperature oxide (LTO), substrates. Hexamethyldisilazane (HMDS)typically provides adhesion to silicon (Si) or silicon oxide (SiO₂)substrates by methylation, but there are apparent limitations as HMDSprimed substrates still show more pattern collapse than printing thesame features on SiARCs. In summation, it has been determined thatresist adhesion following HMDS priming is marginal for high resolutionpatterning, i.e., sub-40P.

The methods and structures described herein provide for an ultrathin,e.g., less than 5 nm, inorganic hardmask, e.g., amorphous Si (α-Si) orlow temperature oxide (LTO), as a direct etch transfer for layer for EUVpatterning. The masks provided herein provide an improvement in resistthickness budget, higher etch selectivity, lower line width roughness(LWR), improved defect elimination, and wet strippability.

It has been determined that amorphous silicon (α-Si) or crystallinesilicon (c-Si) can be stripped off its native oxide layer (SiOx) withdilute hydrofluoric (HF) acid, thereby converting the terminal surfacefunctionality from polar (Si—OH) to non-polar (Si—H). It has furtherbeen determined that the patterning performance with negative tonedevelopment (NTD) or corresponding photoresists is improved withnon-polar (Si—H) surfaces in comparison to hexamethyldisilazane (HMDS)primed surfaces. The increase in patterning performance that is achievedthrough converting a terminal surface functionality from being a polar(Si—OH) surface to a non-polar (Si—H) surface. As will be described ingreater detail below, to convert the terminal surface to a non-polar(Si—H) surface, the surface may be treated with a dilute hydrofluoric(dHF) acid rinse. It has been determined that when an amorphous silicon(α-Si) surface is treated with dHF to generate a surface that isterminated with silicon hydrogen (Si—H) bonds, negative tone development(NTD) resists patterned using extreme ultra violet (EUV) lithographyprovided significantly better patterning performance than when amorphoussilicon (Si) is treated with HDMS prior to resist coating. Exemplaryapplications/uses to which the present invention can be applied include,but are not limited to: digital logic devices (e.g., AND gates, NANDgates, NOR gates, etc.), and memory devices (e.g., SRAM, DRAM, etc.).The methods and structure of the present disclosure are now describedwith greater detail with reference to FIGS. 1-6.

In some embodiments, the method can begin with providing an amorphoussemiconductor surface to be etched, and terminating the surface of anamorphous semiconductor layer 10 by forming silicon-hydrogen (Si—H)bonds 15 on the surface S1 to be patterned at Step 1 of the process flowdepicted in FIG. 1, as illustrated in FIG. 2. The term “amorphous”denotes that the semiconductor material does not have a regularrepeating crystalline structure. The amorphous semiconductor layer 10may be entirely amorphous, e.g., amorphous silicon (α-Si) and may alsoinclude an amorphous matrix with islands of crystalline material, suchas in microcrystalline silicon or nanocrystalline silicon. Although FIG.2 depicts that the amorphous semiconductor layer 10 is an independentlayer, other embodiments have been contemplated in which the amorphouslayer is a component of a material stack of other semiconductormaterials, such as type IV and type III-V semiconductor materials, thatmay have crystalline, e.g., single crystalline, or amorphous crystalstructures; or the amorphous semiconductor layer 10 may be present atopa supporting substrate, which may be composed of a semiconductormaterial, e.g., type IV and/or type III-V. It is not required that thesupporting substrate be composed of semiconductor material, as otherdielectric materials, such as oxides, nitrides and glass compositions,and metal materials may be suitable for providing a supporting substratefor the amorphous semiconductor layer 10. In some examples, thesupporting substrate for the amorphous semiconductor layer 10 may be apolymeric material.

The surface of the amorphous semiconductor layer 10 may be treated toterminate the semiconductor surface S1 with hydrogen bonded to thesemiconductor surface S1. For example, when the amorphous semiconductorlayer 10 is composed of amorphous silicon (α-Si), the semiconductorsurface S1 may be terminated with silicon hydrogen (Si—H) bonding.

To provide a terminated surface, the surface S1 of the amorphoussemiconductor layer 10 may be treated with a hydrofluoric (HF) basedchemical. In some embodiments, prior to applying the dilute hydrofluoricacid (dHF) rinse, the surface S1 of the amorphous semiconductor layer 10may be cleaned using one of acetone, methanol, and deionized water.

In some embodiments, the surface S1 of the amorphous semiconductor layer10, i.e., a surface composed of amorphous silicon (α-Si), is treatedwith a wet chemical rinse including dilute hydrofluoric acid (dHF),which terminates the amorphous silicon with hydrogen to silicon (Si—H)bonding. It is noted that prior to being terminated withsemiconductor-hydrogen bonding, e.g., silicon-hydrogen (Si—H) bonding,the dilute HF rinse may remove any naturally forming oxide, e.g.,silicon oxide, that may be present on the semiconductor surface S1.

In one example, the dilute hydrofluoric acid (dHF) rinse that is used toterminate the surface S1 of the amorphous semiconductor layer 10 caninclude a very highly diluted HF mixture, e.g., less than 0.1%. Thedilute hydrofluoric (dHF) acid rinse is an aqueous solution. It is notedthat the previous example of a 0.1% diluted HF mixture is only oneexample of a diluted HF (dHF) rinse that is suitable for terminating theamorphous semiconductor layer 10. For example, the dilute HF (dHF) rinsemay include hydrofluoric acid (dHF) in amounts equal to 10%, 5%, 3%, 1%,0.5%, 0.3%, 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%,0.02%, 0.01%, as well as any range including one of the aforementionedexamples for the maximum value of the range, and one of theaforementioned examples for the minimum value of the range. It is notedthat the HF-based chemical is not limited to only the aforementioned dHFsolution. For example, in some embodiments the HF-based chemical may bea buffered hydrofluoric acid (BHF) solution, which is a mixed solutionof dHF and NH₄F.

The HF-based chemical. e.g., dilute hydrofluoric acid (dHF) rinse, maybe applied by dipping the surface S of the amorphous semiconductor layer10 into a dHF bath. In other embodiments, the dilute hydrofluoric acid(dHF) rinse may be applied by pouring. e.g., via curtain pouring, thedHF onto the surface S1 of the amorphous semiconductor layer 10. In yetother embodiments, the dilute hydrofluoric acid (dHF) rinse is appliedby spray and/or brush.

The application of the HF-based chemical, e.g., dilute HF (dHF) rinse,may be at room temperature, e.g., 20° C. or 25° C., at 1 atm. In someembodiments, the temperature for the application of the HF-basedchemical, e.g., dilute HF (dHF) rinse, may be at a temperature elevatedfrom room temperature. For example, in some instances, the temperaturefor the application of the HF-based chemical, e.g., dilute HF (dHF)rinse, can range from 70° C. to 80° C.

As noted above, in addition to terminating the surface S1 with siliconto hydrogen bonding, the application of the HF-based chemical, e.g.,dilute HF (dHF) rinse, typically removes the native oxide that ispresent on the surface S1 of the amorphous semiconductor layer 10.Because the native oxide, e.g. silicon oxide (SiO₂), that is present onthe surface of the amorphous semiconductor layer 10 is relatively thin,e.g., less than 1 nm, the concentration of the HF-based chemistry may bedilute, e.g., dHF, and the time period for the application of theHF-based chemical, e.g., dHF, may be relatively short. For example, theprocessing time for the application of the HF-based chemical, e.g., dHF,that removes the native oxide and terminates the surface S1 of theamorphous semiconductor layer 10 may be applied for a time period of 1minute or less. It is noted that the above example is provided forillustrative purposes only, and is not intended to limit the presentdisclosure. For example, the application time for the HF-based chemical.e.g., dilute HF (dHF) rinse, may be equal to 5 seconds, 15 seconds, 30seconds, 1 minute, 2 minutes, 3 minutes, 5 minutes, 10 minutes, 15minutes, 30 minutes and 1 hour, as well as any range including one ofthe aforementioned examples for the maximum value of the range, and oneof the aforementioned examples for the minimum value of the range.

Following application of the HF-based chemical, e.g., dHF, that removesthe native oxide and terminates the surface S1 of the amorphoussemiconductor layer 10, the now terminated surface S1 of the amorphoussemiconductor layer 10 may be rinsed with deionized water. In someexamples, any acidity may be neutralized using a more basic compositionto neutralize and rinse the terminated surface.

Terminating the surface S1 of the amorphous semiconductor layer 10 maybe characterized as being silicon-hydrogen (Si—H) bond 15 terminated. Bystripping the native oxide with a HF-based chemical rinse, such as dHF,thereby converting the terminal surface functionality from polar (Si—OH)to non-polar (Si—H). Hydrophilic and hydrophobic molecules are alsoknown as polar molecules and non-polar molecules, respectively. The term“hydrophobic” means tending to repel or fail to mix with water. The term“hydrophilic” refers to a surface having a strong affinity for water. Itis noted that termination of the S1 of the amorphous semiconductor layer10 can form silicon-hydrogen (Si—H) bonds in the form of Si—H. ≡SiH,═SiH₂, —SiH₃, or a combination thereof.

Referring to FIG. 1, following termination of the surface S1 of theamorphous semiconductor layer 10 to produce a Si—H bonded surface havingnon-polar characteristics, the method may continue with forming aforming a photoresist layer 20 on the surface S1 to be patterned at step3, as depicted in FIG. 3. The photoresist layer 20 that is deposited issuitable for negative tone development (NTD). The negative tonedevelopment process can employ NTD solvents such as n-butyl acetate,2-heptanone, anisole, methyl benzoate and acetophenone.

Photoresists that can provide the photoresist layer 20 for the negativetone development process, i.e., negative tone development resists(NTDRs), may be phenolic, acrylic or hybrid (phenolic-acrylic)chemically amplified photoresists.

In a first embodiment, a phenolic NTDR can be a copolymer ofpolyhydroxystyrene modified with a ketal-based protecting group or atert-butyloxycarbonyl protecting group. The phenolic NTDR can beformulated by dissolution of the phenolic resin, a suitable photoacidgenerator such as triphenylsulfonium perfluorobutanesulfonate and a basequencher such as tetrabutylammonium lactate in an organic solvent suchas propylene glycol monomethyl ether acetate. The thickness of thedeposited layer may be smaller than 100 nm. For example, the thicknessof the deposited NTDR resist may range from 50 nm to 30 nm in order tomake it suitable for high resolution patterning, i.e., for thepatterning of sub-40 nm pitched structures.

In a second embodiment, an acrylic NTDR can be a copolymer of norbornanelactone methacrylate (NLM) and methyl adamantane methacrylate (MAdMA).The acrylic NTDR can be formulated by dissolution of the acrylic resin,a suitable photoacid generator such as triphenylsulfoniumperfluorobutanesulfonate, and a base quencher, such astetrabutylammonium lactate in an organic solvent such as cyclohexanone.The thickness of the deposited layer may be smaller than 100 nm. Forexample, the thickness of the deposited NTDR resist may range from 50 nmto 30 nm in order to make it suitable for high resolution patterning,i.e., for the patterning of sub-40 nm pitched structures.

In a third embodiment, a hybrid NTDR can be a copolymer ofpolyhydroxystyrene and methyl adamantane methacrylate (MAdMA). Thehybrid NTDR can be formulated by dissolution of the hybrid resin, asuitable photoacid generator such as triphenylsulfoniumperfluorobutanesulfonate and a base quencher such as tetrabutylammoniumlactate in an organic solvent such as propylene glycol monomethyl etheracetate. The thickness of the deposited layer may be smaller than 100nm. For example, the thickness of the deposited NTDR resist may rangefrom 50 nm to 30 nm in order to make it suitable for high resolutionpatterning, i.e., for the patterning of sub-40 nm pitched structures.

It is noted that the above examples of resists suitable for negativetone development (also referred to as NTD resists) are provided forillustrative purposes only, and are not intended to limit the presentdisclosure. Other compositions for NTD resists are also applicable tothe present disclosure including polymers, such as polycarbonates,polyimides, polyesters, polyalkenes, copolymers thereof and combinationsthereof.

In general, any suitable coating process can be used to deliver thephotoresist layer 20 to the terminated surface S1 of the amorphoussemiconductor layer 10. Suitable coating approaches can include, forexample, spin coating, spray coating, dip coating, knife edge coating,printing approaches, such as inkjet printing and screen printing, andthe like. Some of these coating approaches form patterns of coatingmaterial during the coating process, although the resolution availablecurrently from printing or the like has a significantly lower level ofresolution than available from radiation based patterning as describedherein. The coating material can be applied in multiple coating steps toprovide greater control over the coating process. For example, multiplespin coatings can be performed to yield an ultimate coating thicknessdesired. The thickness of the deposited layer may range from 1 nm to 500μm. In some embodiments, the photoresist has a thickness of less than 50nm.

In one embodiment, the photoresist layer may be deposited using spin ondeposition methods, in which the spin rate for the substrate may rangefrom 500 rpm to 10,000 rpm.

Following deposition of the photoresist layer 20, the method maycontinue with heating or evaporation of the solvent to harden thephotoresist layer. The coating process itself can result in theevaporation of a portion of the solvent since many coating processesform droplets or other forms of the coating material with larger surfaceareas and/or movement of the solution that stimulates evaporation. Theloss of solvent tends to increase the viscosity of the coating materialas the concentration of the species in the material increases. Ingeneral, the coating material can be heated prior to radiation exposureto further drive off solvent and promote densification of the coatingmaterial.

While heating is not needed for successful application of the process,it can be desirable to heat the coated substrate to speed the processingand/or to increase the reproducibility of the process. In embodiments inwhich heat is applied to remove solvent, the coating material can beheated to temperatures from 45° C. to 150° C., in further embodimentsfrom 50° C. to 130° C. and in other embodiments from 60° C. to 110° C.The heating for solvent removal can generally be performed for at leastabout 0.1 minute, in further embodiments from about 0.5 minutes to about30 minutes and in additional embodiments from about 0.75 minutes toabout 10 minutes. This heating process may be referred to as post-applybake (PAB).

Referring to FIG. 1, following formation of the photoresist layer 20,the method may continue with lithographically patterning the photoresistlayer using an extreme ultra violet (EUV) method at step 4, asillustrated in FIG. 4. In some examples, a pattern is formed using areticle or photomask 25 and transferred into the photoresist layer 20 onthe terminated surface S1 of the amorphous semiconductor layer 10. Lightis reflected off the multi-mirrored surface of the reticle, which inturn produces a patterned image on the layer of photoresist. Forexample, exposure to light may change the exposed portions 20 a of thephotoresist from a soluble condition to an insoluble one. The unexposedportion 20 b of the photoresist is dissolved by the photoresistdeveloper.

The light source 30 may be an EUV light source, in accordance with oneor more embodiments of the present disclosure. EUV light sourcesdesigned for lithography tools typically have high average power (e.g.,100 W and above) at 2% bandwidth with a central wavelength of 13.5 nm.Such systems typically employ a laser produced plasma (LPP) with a metaltarget (e.g., Sn) and a high power laser (e.g., CO₂ with wavelength of10.6 μm). Such a combination is well suited for achieving highconversion efficiency (up to 4-5% in band) and high average power (about100 W and above). In some embodiments to provide an EUV light source, alaser source is provided for initiating and/or maintaining a plasma. Inthis regard, the laser source may supply the energy required to rapidlyheat the plasma-forming target material to a plasma, which, in turn,emits EUV light, i.e., the light source 30.

In one embodiment, the drive laser source may include, but is notlimited to, one or more drive lasers. The number and type of lasers usedin the drive laser source may depend on a number of factors including,but not limited to, the required power output of the individual lasers,the desired EUV light power output, and the efficiency of the EUV lightgeneration process. As an example, EUV light is used by photolithographymask inspection systems, but such systems do not require the high EUVlight power output of primary photolithography systems. An EUV maskinspection system may only require EUV light in the range of 10 W, butwith high brightness in a small area. In the case of mask inspectionsystems, total laser output in the range of a few kilowatts is needed,with the output being focused onto a small target spot (e.g., less than100 μm in diameter).

The drive source may include any pulsed or modulated illumination sourceknown in the art. For example, the drive laser source may include, butis not limited to, a pulsed laser. In one embodiment, the drive lasersource may include, but is not limited to, one or more solid statelasers. For example, the drive laser source may include, but is notlimited to, one or more Nd:YAG, Er:YAG, Yb:YAG. Ti:Sapphire,Nd:Vanadate, and like lasers. In another embodiment, the drive lasersource may include, but is not limited to, a gas-discharge laser. Forexample, the drive laser source may include, but is not limited to, oneor more excimer lasers. In another embodiment, the drive laser sourcemay include, but is not limited to, any laser system capable of emittinglight having a wavelength less than 1 μm.

In one embodiment, the one or more laser pulses of beam to provide thelight source 30 may include a train of pulses with duration in the rangeof 5 to 50 ns. In another embodiment, the total average power of thebeam outputted by the laser source may be in the range of 1-10 kW. Inanother embodiment, the combination of multiple laser outputs mayinclude triggering multiple lasers synchronously.

Although the light source 30 used for patterning the photoresist istypically an EUV light source, the methods disclosed herein are alsoapplicable to immersion photolithography. e.g., 193 nm lithography, aswell as e-beam lithography.

Referring to FIG. 1, following lithographically patterning thephotoresist layer 20, 20 a, 20 b, the method may continue with a hardbake. In general, the coating material can be heated post-radiationexposure to catalyze the cleavage of the protective group from thenegative tone development resist (NTDR) in order to promote the desiredsolubility switch. This heating process may be referred to aspost-exposure bake (PEB).

In embodiments in which heat is applied to drive the deprotectionreaction of the chemically amplified resist, the coating material can beheated to temperatures from 45° C. to 150° C., in further embodimentsfrom 50° C. to 130° C. and in other embodiments from 60° C. to 110° C.The post-exposure bake (PEB) can generally be performed for at leastabout 0.1 minute, in further embodiments from about 0.5 minutes to about30 minutes and in additional embodiments from about 0.75 minutes toabout 10 minutes. Referring to FIG. 1, following post-exposure baking ofthe photoresist layer 20, 20 a, 20 b, the method may continue with adevelopment step that removes the portions of the photoresist layer 20 bthat were not exposed selectively to the exposed portions of photoresistlayer 20 a at step 5, as illustrated in FIG. 5. Development of the imageinvolves the contact of the patterned photoresist layer 20 including thelatent image to a developer composition 35 to remove the un-irradiatedphotoresist portions 20 b.

In general, the developer composition 35 can be comprised of organicsolvents suitable for the NTD process.

In one embodiment, the developer composition can be n-butyl acetate(n-BA). Commercial n-butyl acetate (n-BA) is available from EastmanChemical Co. In another embodiment., the developer can be 2-heptanone.In a yet another embodiment, the developer can be anisole. In a furtherembodiment, the developer can be methyl benzoate. In yet a furtherembodiment, the developer can be acetophenone. In even furtherembodiments, the developer can consist of mixtures based on organicsolvents of the previous embodiments.

The developer can be applied to the patterned coating material using anyreasonable approach. For example, the developer can be sprayed onto thepatterned coating material. Also, spin coating can be used. Forautomated processing, a puddle method can be used involving the pouringof the developer onto the coating material in a stationary format. Ifdesired, spin rinsing and/or drying can be used to complete thedevelopment process. Suitable rinsing solutions include, for example,ultrapure water, methyl alcohol, ethyl alcohol, propyl alcohol,4-methyl-2-pentanol and combinations thereof. After the image isdeveloped, the coating material is disposed on the substrate as apattern.

As noted above, resist-inorganic hardmask adhesion hindered patterningfidelity. Priming a surface with hexamethyldisilazane (HDMS) was theprior method to improve adhesion and pattern performance on silicon(Si), e.g., amorphous silicon (α-Si), crystalline silicon (c-Si), andcombinations thereof, or silicon oxide, e.g., low temperature oxide(LTO) substrates. As noted above, it has been determined that resistadhesion under these circumstances is marginal for resolution patterningin the sub 40 nm pitch realm (sub-40P). This is especially the case withnegative tone resist development and exposure with extreme ultravioletlithography. It has been determined that using the methods describedabove, amorphous silicon (α-Si) or crystalline silicon (c-Si) can bestripped of their native oxide, e.g., silicon oxide, without HDMS usingthe an HF-based chemical, such as dilute HF, thereby converting theterminal surface functionality from polar (SiOH) to non-polar (Si—H),similar to the surface functionality provided by the above describeddilute HF including process. In some embodiments, the patterningperformance with negative tone development (NTD) of correspondingphotoresists is improved with the silicon hydrogen (Si—H) bonded surfacein comparison to the patterning performance of similarly preparedphotoresists formed over surfaces treated with hexamethyldisilazane(HDMS). The performance increase provided by the HF including chemicalsurface treatment, e.g., dilute HF (dHF), is applicable to extremeultraviolet (EUV) photolithography, but is also applicable to immersionphotolithography. e.g., 193 nm lithography, as well as e-beamlithography

FIG. 6A is a scanning electron microscope (SEM) image of a negative tonedeveloped resist that was formed on an amorphous silicon surface thatwas pretreated with hexamethyldisilazane (HDMS) prior to forming thephotoresist layer. The pattern depicted in FIG. 6A is a comparativeexample. FIG. 6B is a scanning electron microscope (SEM) image of anegative tone developed resist that was formed on an amorphous siliconsurface that was pretreated with dilute hydrofluoric acid (dHF) prior toforming photoresist layer, as illustrated above in accordance withprocess flow described with reference to FIG. 1. Both wafers depicted inFIGS. 6A and 6B were coated with an EUV NTD resist followed by an e-beamexposure of P40 equal line/space patterns. The wafers were subsequentlypost-exposure baked and developed using n-butyl acetate (n-BA). Thecomparative example depicted in FIG. 6A illustrates merger of the linesindicative of poor adhesion and lift off. The example depicted in FIG.6B is a set of parallel lines having no merger, which is indicative ofgood adhesion and substantially eliminated lift off when compared to thephotoresist lines depicted in FIG. 6A.

Referring to FIG. 1, following development of the lithographicallypatterning the photoresist layer, the method may continue with etchingthe underlying amorphous semiconductor layer 10 at step 6, asillustrated in FIG. 7. The etch process for etching the underlyingsemiconductor layer 10 is selective to the remaining portions of thephotoresist layer 20 a that provide a photoresist mask. As used herein,the term “selective” in reference to a material removal process denotesthat the rate of material removal for a first material is greater thanthe rate of removal for at least another material of the structure towhich the material removal process is being applied. For example, in oneembodiment, a selective etch may include an etch chemistry that removesa first material selectively to a second material by a ratio of 100:1 orgreater.

In one embodiment, the semiconductor layer 10 may be etched using ananisotropic etch. As used herein, an “anisotropic etch process” denotesa material removal process in which the etch rate in the directionnormal to the surface to be etched is greater than in the directionparallel to the surface to be etched. The anisotropic etch may bereactive ion etching (RIE). Reactive Ion Etching (RIE) is a form ofplasma etching in which during etching the surface to be etched isplaced on the RF powered electrode. Moreover, during RIE the surface tobe etched takes on a potential that accelerates the etching speciesextracted from plasma toward the surface, in which the chemical etchingreaction is taking place in the direction normal to the surface. Otherexamples of anisotropic etching that can be used at this point of thepresent invention include ion beam etching, plasma etching or laserablation.

In some embodiments, the semiconductor layer 10 is etched to provide anultrathin, e.g., less than 5 nm thick, patterned inorganic hardmask,e.g., a patterned inorganic hardmask composed of amorphous silicon(α-Si). The methods and structures disclosed herein may also be used toform a patterned hard mask that is composed of low temperature oxide(LTO) material.

The methods and structures described herein provide better resistthickness budget, higher etch selectively, lower line width roughness(LWR), improved defectivity, and increased wet strippability ofmaterials used in photolithography processes.

Reference in the specification to “one embodiment” or “an embodiment”,as well as other variations thereof, means that a particular feature,structure, characteristic, and so forth described in connection with theembodiment is included in at least one embodiment. Thus, the appearancesof the phrase “in one embodiment” or “in an embodiment”, as well anyother variations, appearing in various places throughout thespecification are not necessarily all referring to the same embodiment.

The present embodiments can include a design for an integrated circuitchip, which can be created in a graphical computer programming language,and stored in a computer storage medium (such as a disk, tape, physicalhard drive, or virtual hard drive such as in a storage access network).If the designer does not fabricate chips or the photolithographic masksused to fabricate chips, the designer can transmit the resulting designby physical means (e.g., by providing a copy of the storage mediumstoring the design) or electronically (e.g., through the Internet) tosuch entities, directly or indirectly. The stored design is thenconverted into the appropriate format (e.g., GDSII) for the fabricationof photolithographic masks, which typically include multiple copies ofthe chip design in question that are to be formed on a wafer. Thephotolithographic masks are utilized to define areas of the wafer(and/or the layers thereon) to be etched or otherwise processed.

Methods as described herein can be used in the fabrication of integratedcircuit chips. The resulting integrated circuit chips can be distributedby the fabricator in raw wafer form (that is, as a single wafer that hasmultiple unpackaged chips), as a bare die, or in a packaged form. In thelatter case, the chip is mounted in a single chip package (such as aplastic carrier, with leads that are affixed to a motherboard or otherhigher level carrier) or in a multichip package (such as a ceramiccarrier that has either or both surface interconnections or buriedinterconnections). In any case, the chip is then integrated with otherchips, discrete circuit elements, and/or other signal processing devicesas part of either (a) an intermediate product, such as a motherboard, or(b) an end product. The end product can be any product that includesintegrated circuit chips, ranging from toys and other low-endapplications to advanced computer products having a display, a keyboardor other input device, and a central processor.

It should also be understood that material compounds will be describedin terms of listed elements, e.g., SiGe. These compounds includedifferent proportions of the elements within the compound, e.g., SiGeincludes Si_(x)Ge_(1-x) where x is less than or equal to 1, etc. Inaddition, other elements can be included in the compound and stillfunction in accordance with the present principles. The compounds withadditional elements will be referred to herein as alloys.

It is to be appreciated that the use of any of the following “/”,“and/or”, and “at least one of”, for example, in the cases of “A/B”, “Aand/or B” and “at least one of A and B”, is intended to encompass theselection of the first listed option (A) only, or the selection of thesecond listed option (B) only, or the selection of both options (A andB). As a further example, in the cases of “A, B. and/or C” and “at leastone of A, B, and C”, such phrasing is intended to encompass theselection of the first listed option (A) only, or the selection of thesecond listed option (B) only, or the selection of the third listedoption (C) only, or the selection of the first and the second listedoptions (A and B) only, or the selection of the first and third listedoptions (A and C) only, or the selection of the second and third listedoptions (B and C) only, or the selection of all three options (A and Band C). This can be extended, as readily apparent by one of ordinaryskill in this and related arts, for as many items listed.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of exampleembodiments. As used herein, the singular forms “a.” “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises,” “comprising.” “includes” and/or “including,” when usedherein, specify the presence of stated features, integers, steps,operations, elements and/or components, but do not preclude the presenceor addition of one or more other features, integers, steps, operations,elements, components and/or groups thereof.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper,” and the like, can be used herein for ease of description todescribe one element's or feature's relationship to another element(s)or feature(s) as illustrated in the FIGS. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the FIGS. For example, if the device in theFIGS. is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the term “below” can encompass both an orientation ofabove and below. The device can be otherwise oriented (rotated 90degrees or at other orientations), and the spatially relativedescriptors used herein can be interpreted accordingly. In addition, itwill also be understood that when a layer is referred to as being“between” two layers, it can be the only layer between the two layers,or one or more intervening layers can also be present.

It will also be understood that when an element such as a layer, regionor substrate is referred to as being “on” or “over” another element, itcan be directly on the other element or intervening elements can also bepresent. In contrast, when an element is referred to as being “directlyon” or “directly over” another element, there are no interveningelements present. It will also be understood that when an element isreferred to as being “connected” or “coupled” to another element, it canbe directly connected or coupled to the other element or interveningelements can be present. In contrast, when an element is referred to asbeing “directly connected” or “directly coupled” to another element,there are no intervening elements present.

It will be understood that, although the terms first, second, etc. canbe used herein to describe various elements, these elements should notbe limited by these terms. These terms are only used to distinguish oneelement from another element. Thus, a first element discussed belowcould be termed a second element without departing from the scope of thepresent concept.

Having described preferred embodiments of a device and method (which areintended to be illustrative and not limiting), it is noted thatmodifications and variations can be made by persons skilled in the artin light of the above teachings. It is therefore to be understood thatchanges may be made in the particular embodiments disclosed which arewithin the scope of the invention as outlined by the appended claims.Having thus described aspects of the invention, with the details andparticularity required by the patent laws, what is claimed and desiredprotected by Letters Patent is set forth in the appended claims.

1. A patterning method comprising: providing a semiconductor surface tobe patterned; terminating the semiconductor surface by formingsilicon-hydrogen (Si—H) bonds on the surface to be patterned; forming aphotoresist on the surface to be patterned; patterning the photoresistlithographically using an extreme ultra violet (EUV) method; anddeveloping the photoresist on the surface to be patterned using negativetone development (NTD).
 2. The method of claim 1, wherein thesemiconductor surface comprises amorphous silicon.
 3. The method ofclaim 1, wherein said terminating the semiconductor surface comprisesapplying an HF-including chemistry.
 4. The method of claim 3, whereinthe HF-including chemistry is dilute hydrofluoric acid.
 5. The method ofclaim 1, wherein said terminating the semiconductor surface comprisesconverting the surface from polar to non-polar.
 6. The method of claim1, wherein said terminating the semiconductor surface further comprisesremoving a native oxide.
 7. The method of claim 1, wherein the formingthe photoresist comprises spin on deposition.
 8. The method of claim 7,wherein said photoresist is phenolic, acrylic or hybrid chemicallyamplified photoresist.
 9. The method of claim 1, wherein the negativetone development (NTD) uses developer comprised of n-butyl acetate(n-BA), 2-heptanone, anisole, methyl benzoate, acetophenone, or mixturesthereof.
 10. A patterning method comprising: providing an amorphoussemiconductor surface to be patterned; applying a dilute hydrofluoricacid (dHF) to the surface to be patterned to terminate the amorphoussemiconductor surface with silicon-hydrogen bonds; forming a photoresiston the surface to be patterned; patterning the photoresistlithographically using an extreme ultra violet (EUV) method; anddeveloping the photoresist on the surface to be patterned using negativetone development (NTD).
 11. The method of claim 10, wherein saidapplying the dilute hydrofluoric acid (dHF) to the surface to bepatterned removes a native oxide.
 12. (canceled)
 13. The method of claim10, wherein said terminating the amorphous semiconductor surfacecomprises converting the surface from polar to non-polar.
 14. The methodof claim 10, wherein the forming the photoresist comprises spin ondeposition.
 15. The method of claim 10, wherein said developingcomprises applying n-butyl acetate (n-BA), 2-heptanone, anisole, methylbenzoate, acetophenone, or mixtures thereof. 16.-20. (canceled)